EP0222988B1 - Process for the preparation of hydroxymethyl propane (cyclopropyl methanol) - Google Patents

Process for the preparation of hydroxymethyl propane (cyclopropyl methanol) Download PDF

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Publication number
EP0222988B1
EP0222988B1 EP86111694A EP86111694A EP0222988B1 EP 0222988 B1 EP0222988 B1 EP 0222988B1 EP 86111694 A EP86111694 A EP 86111694A EP 86111694 A EP86111694 A EP 86111694A EP 0222988 B1 EP0222988 B1 EP 0222988B1
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Prior art keywords
process according
cyclopropanecarboxylic acid
hydrogenated
hydroxymethylcyclopropane
bar
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EP86111694A
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German (de)
French (fr)
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EP0222988A1 (en
Inventor
Werner Dr. Otte
Rudolf Dr. Nehring
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Huels AG
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Huels AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/13—Monohydroxylic alcohols containing saturated rings
    • C07C31/133—Monohydroxylic alcohols containing saturated rings monocyclic
    • C07C31/1333—Monohydroxylic alcohols containing saturated rings monocyclic with a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to a process for the selective production of hydroxymethylcyclopropane from esters of cyclopropanecarboxylic acid in the presence of commercially available zinc chromite catalysts.
  • Hydroxymethylcyclopropane is a known chemical that is used as an intermediate for synthesis, for example of bactericides, fungicides, herbicides and insecticides.
  • hydroxymethylcyclopropane is obtained from cyclopropanecarboxylic acid in the presence of lithium alanate (Beilstein E IV 6, p. 4) or by reacting cyclopropanecarboxylic acids with organometallic compounds in the presence of electrophilic compounds (US Pat. No. 4,085,173. US Pat. No. 4,085,273, US Pat 4,054,480, U.S. Patent 3,998,899, U.S. Patent 3,959,324) or by anodic oxidation of cyclobutane carboxylic acid (J. Am. Chem. Soc. 82, pp. 2645 to 2646 (1960)).
  • the object was therefore to find an economical process for the preparation of hydroxymethylcyclopropane which dispenses with the use of expensive and not easily handled chemicals and which gives the hydroxymethylcyclopropane in high yield.
  • the process according to the invention is carried out at a temperature of 200 to 350 ° C., preferably in the temperature range from 250 to 300 ° C., in particular from 240 to 300 ° C.
  • a hydrogen pressure above 200 bar from 200 to 320 bar, preferably from 240 to 300 bar, is used in the process according to the invention.
  • the cyclopropanecarboxylic acid esters whose alcohol component has 1 to 10, preferably 1 to 8, carbon atoms are particularly suitable as the starting product.
  • the process according to the invention is carried out without using a solvent, but the presence of a solvent is not harmful.
  • a commercial zinc chromite catalyst (e.g. BASF S5-10) is used in the process according to the invention.
  • Suitable zinc chromite catalysts generally contain 40 to 80% by weight of ZnO and 10 to 40% by weight of Cr 2 0 a .
  • the CuCr contacts usually used for the hydrogenation of carboxylic acid esters lead to almost complete conversion to n-butanol and only too little hydroxymethylcyclopropane.
  • the process according to the invention can be carried out batchwise or continuously in a conventional manner, e.g. B. in a stirred autoclave or a reaction tube.
  • the equipment required for the hydrogenation is state of the art.
  • the process according to the invention is carried out in the bottom phase or trickle phase.
  • the bottom phase is usually carried out in an autoclave in the presence of a powdered catalyst.
  • the process according to the invention can be carried out particularly advantageously continuously. This is done in the usual way by passing the liquid starting product over the catalyst arranged in the reaction tube, in accordance with the trickle phase principle, while the hydrogen is passed through the reaction tube in cocurrent or countercurrent. The excess hydrogen is advantageously circulated.
  • the hydrogenation discharge has the following composition:
  • the hydrogenation discharge has the following composition:
  • concentrations given in the examples are determined by gas chromatography and relate to area percent.

Abstract

For the selective production of hydroxymethylcyclopropane, cyclopropanecarboxylic acid esters are hydrogenated in the presence of a Zn chromite catalyst in the sump phase or trickling phase under a hydrogen pressure of 200-320 bar and at temperatures of 200 DEG -350 DEG C. Preferably, cyclopropanecarboxylic acid esters are used, the alcohol component of which contains 1-10, especially 1-8 carbon atoms.

Description

Die Erfindung betrifft ein Verfahren zur selektiven Herstellung von Hydroxymethylcyclopropan aus Estern der Cyclopropancarbonsäure in Gegenwart handelsüblicher Zinkchromit-Katalysatoren. Hydroxymethylcyclopropan ist eine bekannte Chemikalie, die als Zwischenprodukt zur Synthese, beispielsweise von Baktericiden, Fungiciden, Herbiciden und Insekticiden verwendet wird.The invention relates to a process for the selective production of hydroxymethylcyclopropane from esters of cyclopropanecarboxylic acid in the presence of commercially available zinc chromite catalysts. Hydroxymethylcyclopropane is a known chemical that is used as an intermediate for synthesis, for example of bactericides, fungicides, herbicides and insecticides.

Nach bekannten Verfahren erhält man Hydroxymethylcyclopropan aus Cyclopropancarbonsäure in Gegenwart von Lithiumalanat (Beilstein E IV 6, S. 4) oder durch Umsetzungen von Cyclopropancarbonsäuren mit metallorganischen Verbindungen in Gegenwart elektrophiler Verbindungen (US-PS 4085173. US-PS 4 085 273, US-PS 4 054 480, US-PS 3 998 899, US-PS 3 959 324) oder durch anodische Oxidation von Cyclobutancarbonsäure (J. Am. Chem. Soc. 82, S. 2645 bis 2646 (1960)).According to known processes, hydroxymethylcyclopropane is obtained from cyclopropanecarboxylic acid in the presence of lithium alanate (Beilstein E IV 6, p. 4) or by reacting cyclopropanecarboxylic acids with organometallic compounds in the presence of electrophilic compounds (US Pat. No. 4,085,173. US Pat. No. 4,085,273, US Pat 4,054,480, U.S. Patent 3,998,899, U.S. Patent 3,959,324) or by anodic oxidation of cyclobutane carboxylic acid (J. Am. Chem. Soc. 82, pp. 2645 to 2646 (1960)).

Diese Verfahren sind recht aufwendig und bedürfen zu ihrer Ausführung einiger komplizierter und teurer Chemikalien, die in ihrer Handhabung nicht unkritisch sind, außerdem sind die Ausbeuten nur mäßig.These processes are quite complex and require some complicated and expensive chemicals to be carried out, which are not uncritical in their handling, and the yields are only moderate.

Es bestand daher die Aufgabe, ein wirtschaftliches Verfahren zur Herstellung von Hydroxymethylcyclopropan zu finden, das auf den Einsatz teurer und nicht leicht zu handhabender Chemikalien verzichtet sowie das Hydroxymethylcyclopropan in hoher Ausbeute ergibt.The object was therefore to find an economical process for the preparation of hydroxymethylcyclopropane which dispenses with the use of expensive and not easily handled chemicals and which gives the hydroxymethylcyclopropane in high yield.

Diese Aufgabe wird erfindungsgemäß entsprechend den Angaben der Patentansprüche gelöst.This object is achieved according to the invention in accordance with the details of the claims.

Überraschenderweise wurde gefunden, daß bei dem erfindungsgemäßen Verfahren Hydroxymethylcyclopropan in nahezu quantitativer Ausbeute bei annähernd vollständigem Umsatz erhalten wird.Surprisingly, it was found that in the process according to the invention hydroxymethylcyclopropane is obtained in almost quantitative yield with almost complete conversion.

Das erfindungsgemäße Verfahren wird bei einer Temperatur von 200 bis 350 °C, vorzugsweise im Temperaturbereich von 250 bis 300 °C, insbesondere von 240 bis 300 °C durchgeführt.The process according to the invention is carried out at a temperature of 200 to 350 ° C., preferably in the temperature range from 250 to 300 ° C., in particular from 240 to 300 ° C.

Ferner wendet man bei dem erfindungsgemäßen Verfahren einen Wasserstoffdruck oberhalb von 200 bar, von 200 bis 320 bar, vorzugsweise von 240 bis 300 bar, an. Als Einsatzprodukt eignen sich insbesondere die Gyclopropancarbonsäureester, deren Alkoholkomponente 1 bis 10, vorzugsweise 1 bis 8 C-Atome, aufweisen.Furthermore, a hydrogen pressure above 200 bar, from 200 to 320 bar, preferably from 240 to 300 bar, is used in the process according to the invention. The cyclopropanecarboxylic acid esters whose alcohol component has 1 to 10, preferably 1 to 8, carbon atoms are particularly suitable as the starting product.

Im allgemeinen wird das erfindungsgemäße Verfahren ohne Verwendung eines Lösemittels durchgeführt, jedoch ist die Anwesenheit eines Lösemittels nicht schädlich.In general, the process according to the invention is carried out without using a solvent, but the presence of a solvent is not harmful.

Bei dem erfindungsgemäßen Verfahren wird ein handelsüblicher Zinkchromit-Katalysator (z. B. BASF S5-10) eingesetzt. Geeignete Zinkchromit-Katalysatoren enthalten im allgemeinen 40 bis 80 Gew.-% ZnO und 10 bis 40 Gew.-% Cr20a. Die üblicherweise zur Hydrierung von Carbonsäureestern eingesetzten CuCr-Kontakte führen bei nahezu vollständigem Umsatz überwiegend zu n-Butanol und nur zu wenig Hydroxymethylcyclopropan.A commercial zinc chromite catalyst (e.g. BASF S5-10) is used in the process according to the invention. Suitable zinc chromite catalysts generally contain 40 to 80% by weight of ZnO and 10 to 40% by weight of Cr 2 0 a . The CuCr contacts usually used for the hydrogenation of carboxylic acid esters lead to almost complete conversion to n-butanol and only too little hydroxymethylcyclopropane.

Das erfindungsgemäße Verfahren kann sowohl diskontinuierlich als auch kontinuierlich in üblicher Weise ausgeführt werden, z. B. in einem Rührautoklaven oder einem Reaktionsrohr. Die zur Hydrierung erforderlichen Apparaturen sind Stand der Technik. Das erfindungsgemäße Verfahren führt man in der Sumpfphase oder Rieselphase durch.The process according to the invention can be carried out batchwise or continuously in a conventional manner, e.g. B. in a stirred autoclave or a reaction tube. The equipment required for the hydrogenation is state of the art. The process according to the invention is carried out in the bottom phase or trickle phase.

Bei diskontinuierlich betriebenem Verfahren wird üblicherweise in der Sumpfphase in einem Autoklaven in Gegenwart eines pulverförmigen Katalysators gearbeitet. Besonders vorteilhaft läßt sich das erfindungsgemäße Verfahren kontinuierlich ausführen. Dies erfolgt in üblicher Weise dadurch, daß man das flüssige Ausgangsprodukt über den im Reaktionsrohr befindlichen stückig angeordneten Katalysator, nach dem Rieselphasenprinzip, führt, während der Wasserstoff im Gleich- oder Gegenstrom durch das Reaktionsrohr geleitet wird. Vorteilhafterweise wird der überschüssige Wasserstoff im Kreis geführt.In the case of a batch process, the bottom phase is usually carried out in an autoclave in the presence of a powdered catalyst. The process according to the invention can be carried out particularly advantageously continuously. This is done in the usual way by passing the liquid starting product over the catalyst arranged in the reaction tube, in accordance with the trickle phase principle, while the hydrogen is passed through the reaction tube in cocurrent or countercurrent. The excess hydrogen is advantageously circulated.

Die besonderen Vorteile des erfindungsgemäßen Verfahrens liegen in der Einfachheit der Durchführung und der Wirtschaftlichkeit.The particular advantages of the method according to the invention lie in the simplicity of implementation and the economy.

Beispiel 1example 1

Durch ein Reaktionsrohr, gefüllt mit 400 ml Zn-Chromit-Kontakt. werden stündlich 100 ml Cyclopropancarbonsäuremethylester und 400 NI Wasserstoff geführt. Die Temperatur beträgt 270 °C und der Druck 300 bar. Im Hydrieraustrag sind enthalten.

Figure imgb0001
Through a reaction tube filled with 400 ml Zn-Chromit contact. 100 ml of cyclopropanecarboxylic acid methyl ester and 400 NI of hydrogen are passed every hour. The temperature is 270 ° C and the pressure is 300 bar. Are included in the hydrogenation discharge.
Figure imgb0001

Beispiel 2Example 2

Ausführung wie Beispiel 1, jedoch wird Cyclopropancarbonsäure-n-butyl-ester eingesetzt. Der Hydrieraustrag setzt sich wie folgt zusammen :

Figure imgb0002
Execution as example 1, but cyclopropanecarboxylic acid n-butyl ester is used. The Hydrogen discharge is composed as follows:
Figure imgb0002

Beispiel 3Example 3

Ausführung wie Beispiel 1, jedoch wird Cyclopropancarbonsäure-2-ethylhexylester eingesetzt. Der Hydrieraustrag hat folgende Zusammensetzung :

Figure imgb0003
Execution as example 1, but cyclopropanecarboxylic acid 2-ethylhexyl ester is used. The hydrogenation discharge has the following composition:
Figure imgb0003

Beispiel 4Example 4

Ausführung wie Beispiel 3, jedoch wird die Temperatur auf 300 °C erhöht. Der Hydrieraustrag hat folgende Zusammensetzung :

Figure imgb0004
Design as example 3, but the temperature is increased to 300 ° C. The hydrogenation discharge has the following composition:
Figure imgb0004

Beispiel 5Example 5

Ausführung wie Beispiel 3, jedoch wird die Temperatur auf 250 °C erniedrigt. Der Hydrieraustrag hat folgende Zusammensetzung :

Figure imgb0005
Execution as example 3, but the temperature is reduced to 250 ° C. The hydrogenation discharge has the following composition:
Figure imgb0005

VergleichsbeispielComparative example

Ausführung wie Beispiel 1, jedoch wird anstelle eines ZnCr- ein CuCr-Katalysator (HARSHAW 1107) eingesetzt und die Reaktionstemperatur auf 210 °C gesenkt. Der Hydrieraustrag hat folgende Zusammensetzung :

Figure imgb0006
Execution as example 1, however a CuCr catalyst (HARSHAW 1107) is used instead of a ZnCr and the reaction temperature is lowered to 210 ° C. The hydrogenation discharge has the following composition:
Figure imgb0006

Die in den Beispielen angegebenen Konzentrationen sind durch Gaschromatographie bestimmt und beziehen sich auf Flächenprozent.The concentrations given in the examples are determined by gas chromatography and relate to area percent.

Claims (7)

1. A process for the selective preparation of hydroxymethylcyclopropane from a cyclopropanecarboxylic acid ester, characterised in that the cyclopropanecarboxylic acid ester is hydrogenated in the presence of a zinc chromite catalyst in the bottom phase and trickle phase under a hydrogen pressure of 200 to 320 bar and temperature of 200 to 350 °C.
2. A process according to claim 1, characterised in that hydrogenation is performed under a hydrogen pressure of 240 to 300 bar.
3. A process according to claim 1 or 2, characterised in that hydrogenation is performed at a temperature of 200 to 300 °C, preferably 240 to 300 °C.
4. A process according to any of claims 1 to 3, characterised in that a cyclopropanecarboxylic acid ester of which the alcohol component possesses 1 to 10, preferably 1 to 8, carbon atoms, is employed.
5. A process according to any of claims 1 to 4, characterised in that methyl cyclopropanecarboxylate is hydrogenated.
6. A process according to any of claims 1 to 4, characterised in that n-butyl cyclopropanecarboxylate is hydrogenated.
7. A process according to any of claims 1 to 4, characterised in that 2-ethylhexyl cyclopropanecarboxylate is hydrogenated.
EP86111694A 1985-10-26 1986-08-23 Process for the preparation of hydroxymethyl propane (cyclopropyl methanol) Expired EP0222988B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86111694T ATE36514T1 (en) 1985-10-26 1986-08-23 PROCESS FOR PRODUCTION OF HYDROXYMETHYLCYCLOPROPAN (CYCLOPROPYLMETHANOL).

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3538132 1985-10-26
DE19853538132 DE3538132A1 (en) 1985-10-26 1985-10-26 METHOD FOR PRODUCING HYDROXYMETHYLCYCLOPROPANE (CYCLOPROPYLMETHANOL)

Publications (2)

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EP0222988A1 EP0222988A1 (en) 1987-05-27
EP0222988B1 true EP0222988B1 (en) 1988-08-17

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EP86111694A Expired EP0222988B1 (en) 1985-10-26 1986-08-23 Process for the preparation of hydroxymethyl propane (cyclopropyl methanol)

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US (1) US4720597A (en)
EP (1) EP0222988B1 (en)
JP (1) JPS62106033A (en)
AT (1) ATE36514T1 (en)
DE (2) DE3538132A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19505939A1 (en) * 1995-02-21 1996-08-22 Bayer Ag Process for the preparation of hydroxymethyl-cyclopropane
DE19608852A1 (en) * 1996-03-07 1997-09-11 Huels Chemische Werke Ag Process for the preparation of hydroxymethylcyclopropane
DE19611142A1 (en) * 1996-03-21 1997-09-25 Bayer Ag Process for the preparation of hydroxymethylcyclopropane

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2340688A (en) * 1942-04-13 1944-02-01 Procter & Gamble Process of forming alcohols
US3959324A (en) * 1972-04-26 1976-05-25 The Procter & Gamble Company Alkyltin cyclopropylcarbinylsulfonate
US3998889A (en) * 1973-08-20 1976-12-21 The Procter & Gamble Company Process for producing cyclopropyl substituted organosulfides
US3960907A (en) * 1974-07-17 1976-06-01 Zoecon Corporation Esters of cyclopropyl substituted carboxylic acids
US4036877A (en) * 1975-02-12 1977-07-19 Budapesti Muszaki Egyetem Process for the production of aldehydes
US4065480A (en) * 1975-06-12 1977-12-27 The Procter & Gamble Company Process for preparing substituted cyclopropycarbinyl compounds
US4211727A (en) * 1979-03-15 1980-07-08 Shell Oil Company Reduction of carboxylic acid halides to aldehydes

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Publication number Publication date
ATE36514T1 (en) 1988-09-15
JPH0558609B2 (en) 1993-08-27
US4720597A (en) 1988-01-19
DE3538132A1 (en) 1987-04-30
EP0222988A1 (en) 1987-05-27
DE3660542D1 (en) 1988-09-22
JPS62106033A (en) 1987-05-16

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